JP4830133B2 - Manufacturing method of composite plating material - Google Patents
Manufacturing method of composite plating material Download PDFInfo
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本発明は、複合めっき材およびその製造方法に関し、特に、スイッチやコネクタなどの接点や端子部品などの材料として使用される複合めっき材およびその製造方法に関する。 The present invention relates to a composite plating material and a method for manufacturing the same, and more particularly to a composite plating material used as a material for contacts and terminal parts such as switches and connectors and a method for manufacturing the same.
従来、スイッチやコネクタなどの接点や端子部品などの材料として、摺動過程における加熱による銅や銅合金などの導体素材の酸化を防止するために、導体素材に銀めっきを施した銀めっき材が使用されている。 Conventionally, as a material for contacts and terminal parts such as switches and connectors, a silver plating material in which the conductor material is silver-plated to prevent oxidation of the conductor material such as copper and copper alloy due to heating in the sliding process has been used. in use.
しかし、銀めっきは、軟質で摩耗し易く、一般に摩擦係数が高いため、耐摩耗性が低いという問題がある。この問題を解消するため、銀マトリクス中に黒鉛粒子を分散させた複合材の皮膜を電気めっきにより導体素材上に形成して耐摩耗性を向上させる方法が提案されている（例えば、特許文献１参照）。また、炭素粒子の分散に適した湿潤剤が添加されためっき浴を使用することにより、炭素粒子を含む銀めっき皮膜を製造する方法が提案されている（例えば、特許文献２参照）。さらに、ゾル−ゲル法によって炭素粒子を金属酸化物などでコーティングして、銀と炭素粒子の複合めっき液中における炭素粒子の分散性を高め、めっき皮膜中に複合化する炭素粒子の量を増大する方法が提案されている（例えば、特許文献３参照）。 However, silver plating is soft and easy to wear, and generally has a high coefficient of friction, and thus has a problem of low wear resistance. In order to solve this problem, a method of improving wear resistance by forming a composite film in which graphite particles are dispersed in a silver matrix on a conductor material by electroplating has been proposed (for example, Patent Document 1). reference). In addition, a method for producing a silver plating film containing carbon particles by using a plating bath to which a wetting agent suitable for dispersion of carbon particles is added has been proposed (for example, see Patent Document 2). Furthermore, the carbon particles are coated with a metal oxide or the like by a sol-gel method to increase the dispersibility of the carbon particles in the composite plating solution of silver and carbon particles, and increase the amount of carbon particles to be combined in the plating film. A method has been proposed (see, for example, Patent Document 3).
しかし、特許文献１〜３の方法により製造された複合めっき材であっても、摩擦係数が比較的高く且つ耐摩耗性が比較的低いため、特許文献１〜３の方法により製造された複合めっき材よりもめっき皮膜中の炭素粒子の含有量が多く、摩擦係数が低く且つ優れた耐摩耗性の複合めっき材を提供することが望まれている。 However, even if it is a composite plating material manufactured by the method of patent documents 1-3, since the friction coefficient is comparatively high and abrasion resistance is comparatively low, the composite plating manufactured by the method of patent documents 1-3 It is desired to provide a composite plating material having a higher content of carbon particles in the plating film than that of the material, a low friction coefficient, and excellent wear resistance.
したがって、本発明は、このような従来の問題点を鑑み、めっき皮膜中の炭素粒子の含有量が多く、摩擦係数が低く且つ優れた耐摩耗性の複合めっき材を提供することを目的とする。 Therefore, in view of such conventional problems, an object of the present invention is to provide a composite plating material having a high content of carbon particles in a plating film, a low friction coefficient, and excellent wear resistance. .
本発明者らは、上記課題を解決するために鋭意研究した結果、酸化処理を行った後にシランカップリング処理を施した炭素粒子を銀めっき液に添加して複合めっき液を用意し、この複合めっき液を使用して電気めっきを行って、銀層中に炭素粒子を含む複合材からなる皮膜を素材上に形成することにより、めっき皮膜中の炭素粒子の含有量が多く、摩擦係数が低く且つ優れた耐摩耗性の複合めっき材を製造することができることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors prepared a composite plating solution by adding carbon particles subjected to an oxidation treatment and then a silane coupling treatment to a silver plating solution. By performing electroplating using a plating solution and forming a film made of a composite material containing carbon particles in the silver layer on the material, the content of carbon particles in the plating film is high and the friction coefficient is low. And it discovered that the composite plating material of the outstanding abrasion resistance could be manufactured, and came to complete this invention.
すなわち、本発明による複合めっき材の製造方法は、酸化処理を行った後にシランカップリング処理を施した炭素粒子を銀めっき液に添加して複合めっき液を用意し、この複合めっき液を使用して電気めっきを行うことにより、銀層中に炭素粒子を含む複合材からなる皮膜を素材上に形成することを特徴とする。 That is, the method for producing a composite plating material according to the present invention prepares a composite plating solution by adding carbon particles that have been subjected to an oxidation treatment and then subjected to silane coupling treatment to a silver plating solution, and uses this composite plating solution. By performing electroplating, a film made of a composite material containing carbon particles in the silver layer is formed on the material.
この複合めっき材の製造方法において、シランカップリング処理が、炭素粒子を有機溶媒中に分散させて懸濁させた後にシランカップリング剤を添加する処理であるのが好ましく、シランカップリング剤が、ビニル基、エポキシ基、アミノ基およびメルカプト基からなる群から選ばれる少なくとも一種と、メトキシ基、エトキシ基およびイソプロポキシ基からなる群から選ばれる少なくとも一種とを有するのが好ましい。また、酸化処理が、炭素粒子を水中に懸濁させた後に酸化剤を添加する湿式酸化処理であるのが好ましく、酸化剤が、硝酸、過酸化水素、過マンガン酸カリウム、過硫酸カリウムおよび過塩素酸ナトリウムからなる群から選ばれる酸化剤であるのが好ましい。さらに、銀めっき液が硝酸銀と硝酸アンモニウムを含む銀めっき液であるのが好ましい。 In this method of producing a composite plating material, the silane coupling treatment is preferably a treatment in which a silane coupling agent is added after carbon particles are dispersed and suspended in an organic solvent, and the silane coupling agent is It is preferable to have at least one selected from the group consisting of a vinyl group, an epoxy group, an amino group and a mercapto group and at least one selected from the group consisting of a methoxy group, an ethoxy group and an isopropoxy group. Further, the oxidation treatment is preferably a wet oxidation treatment in which carbon particles are suspended in water and then an oxidizing agent is added. The oxidizing agent is nitric acid, hydrogen peroxide, potassium permanganate, potassium persulfate, and excess. An oxidizing agent selected from the group consisting of sodium chlorate is preferred. Furthermore, the silver plating solution is preferably a silver plating solution containing silver nitrate and ammonium nitrate.
また、本発明による複合めっき液は、素材を銀めっきするための銀めっき液に、酸化処理とシランカップリング処理を施した炭素粒子が添加されていることを特徴とする。 The composite plating solution according to the present invention is characterized in that carbon particles subjected to an oxidation treatment and a silane coupling treatment are added to a silver plating solution for silver plating of a material.
本発明によれば、めっき皮膜中の炭素粒子の含有量が多く、摩擦係数が低く且つ優れた耐摩耗性の複合めっき材を製造することができる。この複合めっき材は、スイッチやコネクタなどの端子の高寿命化に十分に対応可能な材料として使用することができる。 According to the present invention, it is possible to produce a composite plating material having a high content of carbon particles in the plating film, a low friction coefficient, and excellent wear resistance. This composite plating material can be used as a material that can sufficiently cope with the extension of the service life of terminals such as switches and connectors.
本発明による複合めっき材の製造方法の実施形態では、酸化処理を行った後にシランカップリング処理を施した炭素粒子を、硝酸銀と硝酸アンモニウムを含む銀めっき液に添加して複合めっき液とし、この複合めっき液を使用して電気めっきを行うことにより、銀層中に炭素粒子を含む複合材からなる皮膜を素材上に形成する。 In the embodiment of the method for producing a composite plating material according to the present invention, carbon particles subjected to oxidization treatment and silane coupling treatment are added to a silver plating solution containing silver nitrate and ammonium nitrate to form a composite plating solution. By performing electroplating using a plating solution, a film made of a composite material containing carbon particles in a silver layer is formed on the material.
本発明による複合めっき材の製造方法の実施形態では、まず、酸化処理により炭素粒子の表面に吸着している親油性有機物を除去する。このような親油性有機物として、アルカンやアルケンなどの脂肪酸炭化水素や、アルキルベンゼンなどの芳香族炭化水素が含まれる。炭素粒子の酸化処理として、湿式酸化処理の他、Ｏ２ガスなどによる乾式酸化処理を使用することができるが、量産性の観点から湿式酸化処理を使用するのが好ましく、湿式酸化処理によって表面積が大きい炭素粒子を均一に処理することができる。 In the embodiment of the method for producing a composite plating material according to the present invention, first, the lipophilic organic matter adsorbed on the surface of the carbon particles is removed by oxidation treatment. Such lipophilic organic substances include fatty acid hydrocarbons such as alkanes and alkenes, and aromatic hydrocarbons such as alkylbenzenes. As the oxidation treatment of the carbon particles, a dry oxidation treatment using O 2 gas or the like can be used in addition to the wet oxidation treatment, but it is preferable to use the wet oxidation treatment from the viewpoint of mass productivity, and the surface area is increased by the wet oxidation treatment. Large carbon particles can be treated uniformly.
湿式酸化処理の方法としては、炭素粒子を水中に懸濁させた後に適量の酸化剤を添加する方法などを使用することができる。酸化剤としては、硝酸、過酸化水素、過マンガン酸カリウム、過硫酸カリウム、過塩素酸ナトリウムなどの酸化剤を使用することができる。炭素粒子に付着している親油性有機物は、添加された酸化剤により酸化されて水に溶けやすい形態になり、炭素粒子の表面から適宜除去されると考えられる。また、この湿式酸化処理を行った後、ろ過を行い、さらに炭素粒子を水洗することにより、炭素粒子の表面から親油性有機物を除去する効果をさらに高めることができる。 As a wet oxidation method, a method of adding an appropriate amount of an oxidizing agent after suspending carbon particles in water can be used. As the oxidizing agent, oxidizing agents such as nitric acid, hydrogen peroxide, potassium permanganate, potassium persulfate, and sodium perchlorate can be used. It is considered that the lipophilic organic substance adhering to the carbon particles is oxidized by the added oxidizing agent to be easily dissolved in water, and is appropriately removed from the surface of the carbon particles. Moreover, after performing this wet oxidation process, the effect which removes lipophilic organic substance from the surface of a carbon particle can be further heightened by filtering, and also washing | cleaning a carbon particle with water.
上記の酸化処理により炭素粒子の表面から脂肪族炭化水素や芳香族炭化水素などの親油性有機物を除去することができ、３００℃加熱ガスによる分析によれば、酸化処理後の炭素粒子を３００℃で加熱して発生したガス中には、アルカンやアルケンなどの親油性脂肪族炭化水素や、アルキルベンゼンなどの親油性芳香族炭化水素が殆ど含まれてない。酸化処理後の炭素粒子中に脂肪族炭化水素や芳香族炭化水素が若干含まれていても、炭素粒子を銀めっき液に分散させることができるが、炭素粒子中に分子量１６０以上の炭化水素が含まれず且つ炭素粒子中の分子量１６０未満の炭化水素の３００℃加熱発生ガス強度（パージ・アンド・トラップ・ガスクロマトグラフ質量分析強度）が５，０００，０００以下になるのが好ましい。炭素粒子中に分子量の大きな炭化水素が含まれると、炭素粒子の表面が強い親油性の炭化水素で被覆され、水溶液である銀めっき溶液中で炭素粒子が互い凝集し、めっき皮膜中に炭素粒子が複合化しなくなると考えられる。 Lipophilic organic substances such as aliphatic hydrocarbons and aromatic hydrocarbons can be removed from the surface of the carbon particles by the above oxidation treatment, and according to the analysis with 300 ° C. heating gas, the carbon particles after the oxidation treatment are converted to 300 ° C. The gas generated by heating in step 3 hardly contains lipophilic aliphatic hydrocarbons such as alkanes and alkenes and lipophilic aromatic hydrocarbons such as alkylbenzenes. Even if aliphatic hydrocarbons and aromatic hydrocarbons are slightly contained in the oxidized carbon particles, the carbon particles can be dispersed in the silver plating solution. However, hydrocarbons having a molecular weight of 160 or more are contained in the carbon particles. It is preferred that the hydrocarbons not contained and having a molecular weight of less than 160 in the carbon particles have a 300 ° C. heat generation gas intensity (purge and trap gas chromatograph mass spectrometry intensity) of 5,000,000 or less. When hydrocarbons with a large molecular weight are contained in the carbon particles, the surfaces of the carbon particles are coated with strong lipophilic hydrocarbons, and the carbon particles aggregate together in the silver plating solution, which is an aqueous solution, and the carbon particles in the plating film Will not be combined.
次に、酸化処理を行った炭素粒子にシランカップリング処理を施す。このシランカップリング処理の方法として、酸化処理を行った炭素粒子を有機溶媒中に分散させて懸濁させ、この懸濁液に適量のシランカップリング剤を添加する方法を使用することができる。シランカップリング剤としては、有機官能基としてビニル基、エポキシ基、アミノ基、メルカプト基などを有し、加水分解基としてメトキシ基、エトキシ基、イソプロポキシ基などを有するシランカップリング剤を使用することができる。このようなシランカップリング処理を施すことにより、炭素粒子の表面電位が変化して、ゼータ電位の等電点をｐＨ６〜１０に変化させることができる。このシランカップリング処理後の炭素粒子は、ｐＨ６〜１０のめっき液中で正に帯電するため、負に帯電した素材に接近し易くなって、めっきの際の陰極との親和性が向上し、その結果、複合めっき皮膜中の炭素粒子の含有量を増大させることができると考えられる。 Next, the carbon particles subjected to the oxidation treatment are subjected to silane coupling treatment. As a method for this silane coupling treatment, a method can be used in which the oxidized carbon particles are dispersed and suspended in an organic solvent, and an appropriate amount of a silane coupling agent is added to this suspension. As the silane coupling agent, a silane coupling agent having a vinyl group, an epoxy group, an amino group, a mercapto group, or the like as an organic functional group and a methoxy group, an ethoxy group, an isopropoxy group, or the like as a hydrolysis group is used. be able to. By performing such silane coupling treatment, the surface potential of the carbon particles is changed, and the isoelectric point of the zeta potential can be changed to pH 6-10. Since the carbon particles after the silane coupling treatment are positively charged in a plating solution having a pH of 6 to 10, it becomes easy to approach a negatively charged material, and the affinity with the cathode during plating is improved. As a result, it is considered that the content of carbon particles in the composite plating film can be increased.
上記の酸化処理およびシランカップリング処理を施した炭素粒子（ゼータ電位の等電点がｐＨ６〜１０の炭素粒子）を銀めっき液に添加することにより、界面活性剤を添加することなく、炭素粒子が銀めっき液中に均一に分散した複合めっき液が得られる。 By adding the above-mentioned oxidation treatment and silane coupling treatment carbon particles (carbon particles having an isoelectric point of zeta potential of pH 6 to 10) to the silver plating solution, carbon particles can be added without adding a surfactant. A composite plating solution in which is uniformly dispersed in the silver plating solution is obtained.
炭素粒子を添加する銀めっき液としては、ｐＨ６〜１０に調整した硝酸銀と硫酸アンモニウムとピロリン酸ナトリウムとからなるアンモニア系銀めっき液を使用するのが好ましい。この場合、硝酸銀の濃度は、２０〜６０ｇ／Ｌであるのが好ましい。２０ｇ／Ｌ未満では、めっき液中の銀濃度が低いために銀の析出効率が低下し、６０ｇ／Ｌを越えると、硝酸銀の溶解が困難になるからである。また、硫酸アンモニウムの濃度は、１００〜１４０ｇ／Ｌであるのが好ましい。１００ｇ／Ｌ未満では、銀の析出効率が低下し、１４０ｇ／Ｌを越えると、銀が異常に析出し易くなるからである。さらに、ピロリン酸ナトリウムの濃度は、１０〜３０ｇ／Ｌであるのが好ましい。１０ｇ／Ｌ未満では、めっき液の電気伝導度が低下してめっきの析出効率が低下し、３０ｇ／Ｌを越えると、銀めっきの異常析出が生じ易くなるからである。なお、複合めっき液中の炭素粒子の濃度は、４０〜１２０ｇ／Ｌであるのが好ましい。４０ｇ／Ｌ未満では、炭素粒子が複合化する量が著しく低下し、１２０ｇ／Ｌを超えると、複合めっき液の粘度が増大して攪拌が困難になるからである。 As the silver plating solution to which carbon particles are added, it is preferable to use an ammonia-based silver plating solution comprising silver nitrate, ammonium sulfate and sodium pyrophosphate adjusted to pH 6-10. In this case, the concentration of silver nitrate is preferably 20 to 60 g / L. If it is less than 20 g / L, the silver concentration in the plating solution is low, so that the silver deposition efficiency decreases. If it exceeds 60 g / L, it is difficult to dissolve silver nitrate. Moreover, it is preferable that the density | concentration of ammonium sulfate is 100-140 g / L. This is because if the amount is less than 100 g / L, the silver deposition efficiency decreases, and if it exceeds 140 g / L, silver is likely to be abnormally precipitated. Furthermore, the concentration of sodium pyrophosphate is preferably 10 to 30 g / L. This is because if it is less than 10 g / L, the electrical conductivity of the plating solution decreases and the deposition efficiency of the plating decreases, and if it exceeds 30 g / L, abnormal silver plating tends to occur. In addition, it is preferable that the density | concentration of the carbon particle in a composite plating solution is 40-120 g / L. If the amount is less than 40 g / L, the amount of carbon particles to be combined is significantly reduced. If the amount exceeds 120 g / L, the viscosity of the composite plating solution increases and stirring becomes difficult.
上記の複合めっき液を使用することにより、めっき皮膜中の炭素粒子の含有量が多く、摩擦係数が低く且つ優れた耐摩耗性の複合めっき材を製造することができる。めっき皮膜中の炭素粒子の含有量が多くなるのは、複合めっき液が界面活性剤を含まないことにより、めっきの結晶の成長過程における成長面への界面活性剤の吸着がないので、銀マトリックスに炭素粒子が取り込まれ易くなるためであると考えられる。また、摩擦係数が低くなるのは、めっき皮膜中の炭素粒子の含有量が多くなることにより、炭素粒子によるめっき皮膜の表面の潤滑作用が向上するためであると考えられる。 By using the above composite plating solution, it is possible to produce a composite plating material having a high content of carbon particles in the plating film, a low friction coefficient, and excellent wear resistance. The content of carbon particles in the plating film is increased because the composite plating solution does not contain a surfactant, so that there is no adsorption of the surfactant to the growth surface during the growth process of the plating crystal. This is thought to be because carbon particles are easily taken in. Moreover, it is thought that the friction coefficient is lowered because the lubrication action of the surface of the plating film by the carbon particles is improved by increasing the content of the carbon particles in the plating film.
上述した本発明による複合めっき材の製造方法の実施の形態により、銀層中に０．３〜２．０質量％、好ましくは１．５質量％以上の炭素粒子を含有する複合材からなる皮膜が素材上に形成された複合めっき材を製造することができる。また、このようにして製造された複合めっき材の動摩擦係数は、摺動初期で０．１５〜０．２５であり、摺動が進んでも０．２０〜０．２５程度と低い値である。なお、従来の銀めっき材の動摩擦係数は１．０〜１．４程度であり、従来の銀と炭素粒子の複合めっき材の動摩擦係数は０．３０〜０．５０程度である。 According to the embodiment of the method for producing a composite plating material according to the present invention described above, a film comprising a composite material containing 0.3 to 2.0 mass%, preferably 1.5 mass% or more of carbon particles in the silver layer. The composite plating material formed on the material can be manufactured. Moreover, the dynamic friction coefficient of the composite plating material manufactured in this way is 0.15 to 0.25 at the initial stage of sliding, and is a low value of about 0.20 to 0.25 even when sliding progresses. In addition, the dynamic friction coefficient of the conventional silver plating material is about 1.0 to 1.4, and the dynamic friction coefficient of the conventional composite plating material of silver and carbon particles is about 0.30 to 0.50.
また、複合めっき皮膜の厚さは、２〜２０μｍであるのが好ましい。２μｍ未満では、耐摩耗性が不十分であり、２０μｍを越えると、生産効率が悪くなるからである。 Moreover, it is preferable that the thickness of a composite plating film is 2-20 micrometers. If the thickness is less than 2 μm, the wear resistance is insufficient, and if it exceeds 20 μm, the production efficiency deteriorates.
以下、本発明による複合めっき材の製造方法の実施例について詳細に説明する。 Hereinafter, the Example of the manufacturing method of the composite plating material by this invention is described in detail.
［実施例１］
炭素粒子として平均粒径３μｍの鱗片状黒鉛粒子（エスイーシー社製のカーボンＳＧＰ−３）を用意し、この黒鉛粒子６質量％を３Ｌの純水中に添加し、この混合溶液を攪拌しながら５０℃に昇温させた。次に、この混合溶液に酸化剤として０．１モル／Ｌの過硫酸カリウム水溶液１．２Ｌを徐々に滴下した後、２時間攪拌して酸化処理を行い、その後、ろ紙によりろ別を行い、水洗を行った。
[Example 1]
As the carbon particles, scaly graphite particles having an average particle diameter of 3 μm (carbon SGP-3 manufactured by ESC) were prepared, 6% by mass of the graphite particles were added to 3 L of pure water, and the mixed solution was stirred while stirring. The temperature was raised to ° C. Next, 1.2 L of a 0.1 mol / L potassium persulfate aqueous solution as an oxidizing agent was gradually added dropwise to the mixed solution, and then the mixture was stirred for 2 hours for oxidation treatment, and then filtered with a filter paper. Washed with water.
この酸化処理の前後の炭素粒子について、パージ・アンド・トラップ・ガスクロマトグラフ質量分析装置（日本分析工業ＪＨＳ−１００）（島津製作所製のＧＣＭＡＳ ＱＰ−５０５０Ａ）を使用して、３００℃加熱発生ガスの分析を行ったところ、上記の酸化処理により、炭素粒子に付着していたノナン、デカン、３−メチル−２−ヘプテンなどの親油性脂肪族炭化水素や、キシレンなどの親油性芳香族炭化水素が除去され、水分散性の良好な炭素粒子が得られているのがわかった。 About the carbon particles before and after this oxidation treatment, a purge and trap gas chromatograph mass spectrometer (Nippon Analytical Industries JHS-100) (GCMAS QP-5050A manufactured by Shimadzu Corporation) As a result of the analysis, lipophilic aliphatic hydrocarbons such as nonane, decane and 3-methyl-2-heptene and lipophilic aromatic hydrocarbons such as xylene adhering to the carbon particles by the oxidation treatment described above were obtained. It was found that carbon particles with good water dispersibility were obtained.
次に、上記の湿式酸化処理を行った炭素粒子１０質量％をトルエン中に分散させて懸濁させ、この炭素粒子の懸濁液を１２０℃に加熱して攪拌しながら、シランカップリング剤として３−アミノプロピルトリメトキシシラン（トルエンの１体積％）を添加した後、６時間攪拌してシランカップリング処理を行った。その後、炭素粒子をトルエンで洗浄し、１２０℃で２４時間乾燥させた。このように酸化処理およびシランカップリング処理を施した炭素粒子の表面電位について、ゼータ電位計（大塚電子製のＥＬＳ−８０００ＫＷ）を用いて測定したところ、等電点はｐＨ１０であった。 Next, 10% by mass of the carbon particles subjected to the above-described wet oxidation treatment are dispersed and suspended in toluene, and the suspension of the carbon particles is heated to 120 ° C. while stirring and used as a silane coupling agent. After 3-aminopropyltrimethoxysilane (1% by volume of toluene) was added, the mixture was stirred for 6 hours to perform silane coupling treatment. Thereafter, the carbon particles were washed with toluene and dried at 120 ° C. for 24 hours. The surface potential of the carbon particles subjected to oxidation treatment and silane coupling treatment as described above was measured using a zeta potentiometer (ELS-8000 KW manufactured by Otsuka Electronics Co., Ltd.), and the isoelectric point was pH 10.
次に、上記の酸化処理およびシランカップリング処理を施した炭素粒子５０ｇ／Ｌを、硝酸銀４０ｇ／Ｌと硫酸アンモニウム１２０ｇ／Ｌとピロリン酸ナトリウム２０ｇ／Ｌとからなるアンモニア系銀めっき液中に添加して、分散および懸濁させて複合めっき液を作製した。 Next, 50 g / L of carbon particles subjected to the above oxidation treatment and silane coupling treatment are added to an ammonia-based silver plating solution composed of silver nitrate 40 g / L, ammonium sulfate 120 g / L, and sodium pyrophosphate 20 g / L. The composite plating solution was prepared by dispersing and suspending.
この複合めっき液を使用して、液温２５℃、電流密度１．５Ａ／ｄｍ２で電気めっきを行い、素材としての厚さ０．３ｍｍの銅板上に膜厚１０μｍの銀と炭素粒子の複合めっき皮膜が形成された複合めっき材を作製した。なお、めっき膜の密着性を向上させるために、下地めっきとして、硝酸銀０．０３ｇ／Ｌとピロリン酸ナトリウム０．４ｇ／Ｌと硝酸ナトリウム０．８ｇ／Ｌとからなる組成のＡｇストライクめっき浴中において、液温２５℃、電流密度５Ａ／ｄｍ２でＡｇストライクめっきを行った。 Using this composite plating solution, electroplating is performed at a liquid temperature of 25 ° C. and a current density of 1.5 A / dm 2 , and a composite of silver and carbon particles having a thickness of 10 μm is formed on a copper plate having a thickness of 0.3 mm as a material. A composite plating material on which a plating film was formed was produced. In order to improve the adhesion of the plating film, as an undercoat, in an Ag strike plating bath having a composition comprising 0.03 g / L of silver nitrate, 0.4 g / L of sodium pyrophosphate and 0.8 g / L of sodium nitrate. in a liquid temperature 25 ° C., it was Ag strike plating at a current density of 5A / dm 2.
得られた複合めっき材（素材を含む）から切り出した試験片を銀および炭素の分析用にそれぞれ用意し、試験片中の銀の含有量（Ｘ質量％）をＩＣＰ装置（ジャーレル・アッシュ社製のＩＲＩＳ／ＡＲ）を用いてプラズマ分光分析法によって求めるとともに、試験片中の炭素の含有量（Ｙ質量％）を微量炭素・硫黄分析装置（堀場製作所製のＥＭＩＡ−Ｕ５１０）を用いて燃焼赤外線吸収法によって求め、めっき皮膜中の炭素の含有量をＹ／（Ｘ＋Ｙ）として算出したところ、めっき皮膜中の炭素の含有量は１．９質量％であった。 Test pieces cut out from the obtained composite plating material (including raw materials) were prepared for analysis of silver and carbon, respectively, and the content (X mass%) of silver in the test pieces was determined using an ICP device (manufactured by Jarrel Ash). (IRIS / AR), and the content of carbon in the test piece (Y mass%) is determined by combustion infrared using a trace carbon / sulfur analyzer (EMIA-U510 manufactured by Horiba, Ltd.). The carbon content in the plating film was calculated to be Y / (X + Y) by the absorption method, and the carbon content in the plating film was 1.9% by mass.
また、摩擦力測定器付の電気接点シミュレータ（山崎精機研究所製のＣＲＳ−１）を使用し、得られた複合めっき材から切り出した試験片に、厚さ５μｍの銀めっき皮膜を形成した圧子を荷重０．５Ｎで押し付けながら摺動させることにより、複合めっき材の摩擦係数を測定した。その結果、摩擦係数は、摺動初期で０．１５〜０．２５であり、摺動が進んでも０．２０〜０．２５であった。 Moreover, the indenter which formed the silver plating film | membrane with a thickness of 5 micrometers on the test piece cut out from the obtained composite plating material using the electrical contact simulator (CRS-1 by Yamazaki Seiki Laboratory) with a friction force measuring device. Was slid while pressing with a load of 0.5 N, and the friction coefficient of the composite plating material was measured. As a result, the coefficient of friction was 0.15 to 0.25 at the beginning of sliding, and was 0.20 to 0.25 even when sliding progressed.
また、得られた複合めっき材から切り出した２つの試験片の一方をインデント加工（Ｒ３ｍｍ）して圧子とするとともに、他方を評価試料とし、圧子を一定の荷重（０．５Ｎ）で評価試料に押し当てながら、素材が露出するまで往復摺動動作（摺動距離１０ｍｍ、摺動速度２．５Ｈｚ）を継続して、複合めっき材の摩耗状態を確認することにより、耐摩耗性の評価を行った。その結果、５０万回の往復摺動動作後でも素材が露出することはなかった。 In addition, one of the two test pieces cut out from the obtained composite plating material is indented (R3 mm) to form an indenter, the other is used as an evaluation sample, and the indenter is used as an evaluation sample with a constant load (0.5 N). While pressing, continue the reciprocating sliding operation (sliding distance 10 mm, sliding speed 2.5 Hz) until the material is exposed, and evaluate the wear resistance by checking the wear state of the composite plating material. It was. As a result, the material was not exposed even after 500,000 reciprocating sliding operations.
［実施例２］
シランカップリング剤として３−メルカプトプロピルトリメトキシシランを使用した以外は実施例１と同様の方法により、酸化処理およびシランカップリング処理を行った。このように処理した炭素粒子の表面電位について実施例１と同様の方法により測定したところ、等電点はｐＨ８であった。
[Example 2]
Oxidation treatment and silane coupling treatment were performed in the same manner as in Example 1 except that 3-mercaptopropyltrimethoxysilane was used as the silane coupling agent. When the surface potential of the carbon particles thus treated was measured by the same method as in Example 1, the isoelectric point was pH 8.
次に、上記の酸化処理およびシランカップリング処理を行った炭素粒子を使用して、実施例１と同様の方法により複合めっき液を作製した。この複合めっき液を使用して、液温２５℃、電流密度２．５Ａ／ｄｍ２で電気めっきを行い、素材としての厚さ０．３ｍｍの銅板上に膜厚１０μｍの銀と炭素粒子の複合めっき皮膜が形成された複合めっき材を作製した。 Next, a composite plating solution was prepared by the same method as in Example 1 using the carbon particles subjected to the above oxidation treatment and silane coupling treatment. Using this composite plating solution, electroplating is performed at a liquid temperature of 25 ° C. and a current density of 2.5 A / dm 2 , and a composite of silver and carbon particles having a thickness of 10 μm is formed on a copper plate having a thickness of 0.3 mm as a material. A composite plating material on which a plating film was formed was produced.
得られた複合めっき材について、実施例１と同様の方法により、めっき皮膜中の炭素の含有量を算出し、摩擦係数を測定し、耐摩耗性の評価を行った。その結果、めっき皮膜中の炭素の含有量は１．５質量％であり、摩擦係数は、摺動初期で０．２０〜０．３０、摺動が進んでも０．２５〜０．３５であった。また、５０万回の往復摺動動作後でも素材が露出することはなかった。 About the obtained composite plating material, the carbon content in the plating film was calculated by the same method as in Example 1, the friction coefficient was measured, and the wear resistance was evaluated. As a result, the carbon content in the plating film was 1.5% by mass, and the coefficient of friction was 0.20 to 0.30 at the beginning of sliding, and 0.25 to 0.35 even when sliding progressed. It was. Further, the material was not exposed even after 500,000 reciprocating sliding operations.
［実施例３］
シランカップリング処理において溶媒としてエタノールを使用した以外は実施例１と同様の方法により、酸化処理およびシランカップリング処理を施した。このように処理した炭素粒子の表面電位について実施例１と同様の方法により測定したところ、等電点はｐＨ８であった。
[Example 3]
Oxidation treatment and silane coupling treatment were performed in the same manner as in Example 1 except that ethanol was used as a solvent in the silane coupling treatment. When the surface potential of the carbon particles thus treated was measured by the same method as in Example 1, the isoelectric point was pH 8.
次に、上記の酸化処理およびシランカップリング処理を行った炭素粒子を使用して、実施例１と同様の方法により複合めっき液を作製した。この複合めっき液を使用して、液温２５℃、電流密度３．０Ａ／ｄｍ２で電気めっきを行い、素材としての厚さ０．３ｍｍの銅板上に膜厚１０μｍの銀と炭素粒子の複合めっき皮膜が形成された複合めっき材を作製した。 Next, a composite plating solution was prepared by the same method as in Example 1 using the carbon particles subjected to the above oxidation treatment and silane coupling treatment. Using this composite plating solution, electroplating is performed at a liquid temperature of 25 ° C. and a current density of 3.0 A / dm 2 , and a composite of silver and carbon particles having a thickness of 10 μm is formed on a copper plate having a thickness of 0.3 mm as a material. A composite plating material on which a plating film was formed was produced.
得られた複合めっき材について、実施例１と同様の方法により、めっき皮膜中の炭素の含有量を算出し、摩擦係数を測定し、耐摩耗性の評価を行った。その結果、めっき皮膜中の炭素の含有量は１．５質量％であり、摩擦係数は、摺動初期で０．２０〜０．３０、摺動が進んでも０．２５〜０．３０であった。また、５０万回の往復摺動動作後でも素材が露出することはなかった。 About the obtained composite plating material, the carbon content in the plating film was calculated by the same method as in Example 1, the friction coefficient was measured, and the wear resistance was evaluated. As a result, the carbon content in the plating film was 1.5% by mass, and the friction coefficient was 0.20 to 0.30 at the beginning of sliding, and 0.25 to 0.30 even when sliding progressed. It was. Further, the material was not exposed even after 500,000 reciprocating sliding operations.
［比較例１］
シランカップリング処理を行わなかった以外は、実施例１と同様の方法により複合めっき液を作製した。この複合めっき液を使用して、液温２５℃、電流密度２．０Ａ／ｄｍ２で電気めっきを行い、素材としての厚さ０．３ｍｍの銅板上に膜厚２０μｍの銀と炭素粒子の複合めっき皮膜が形成された複合めっき材を作製した。
[Comparative Example 1]
A composite plating solution was prepared in the same manner as in Example 1 except that the silane coupling treatment was not performed. Using this composite plating solution, electroplating is performed at a liquid temperature of 25 ° C. and a current density of 2.0 A / dm 2 , and a composite of silver and carbon particles having a thickness of 20 μm is formed on a copper plate having a thickness of 0.3 mm as a material. A composite plating material on which a plating film was formed was produced.
得られた複合めっき材について、実施例１と同様の方法により、めっき皮膜中の炭素の含有量を算出し、摩擦係数を測定し、耐摩耗性の評価を行った。その結果、めっき皮膜中の炭素の含有量は０．２質量％であり、摩擦係数は、摺動初期で０．７０〜０．８０、摺動が進むと１．０〜１．２になった。また、３千回の往復摺動動作後に素材が露出した。 About the obtained composite plating material, the carbon content in the plating film was calculated by the same method as in Example 1, the friction coefficient was measured, and the wear resistance was evaluated. As a result, the content of carbon in the plating film is 0.2% by mass, and the coefficient of friction is 0.70 to 0.80 at the beginning of sliding, and 1.0 to 1.2 when sliding progresses. It was. The material was exposed after 3,000 reciprocating sliding operations.
［比較例２］
実施例１と同様の方法により炭素粒子を酸化処理した後、炭素粒子の懸濁液の加熱温度を６０℃とし、シランカップリング剤の添加後の攪拌時間を２４時間とし、シランカップリング処理後の炭素粒子の乾燥を７０℃で４８時間行った以外は、実施例１と同様の方法によりシランカップリング処理を行った。このように処理した炭素粒子の表面電位について実施例１と同様の方法により測定したところ、等電点はｐＨ１１であった。
[Comparative Example 2]
After the carbon particles are oxidized by the same method as in Example 1, the heating temperature of the suspension of carbon particles is 60 ° C., the stirring time after the addition of the silane coupling agent is 24 hours, and after the silane coupling treatment A silane coupling treatment was performed in the same manner as in Example 1 except that the carbon particles were dried at 70 ° C. for 48 hours. When the surface potential of the carbon particles thus treated was measured by the same method as in Example 1, the isoelectric point was pH 11.
次に、上記の酸化処理およびシランカップリング処理を施した炭素粒子を使用して、実施例１と同様の方法により複合めっき液を作製した。この複合めっき液を使用して、液温２５℃、電流密度１．５Ａ／ｄｍ２で電気めっきを行い、素材としての厚さ０．３ｍｍの銅板上に膜厚１５μｍの銀と炭素粒子の複合めっき皮膜が形成された複合めっき材を作製した。 Next, a composite plating solution was produced by the same method as in Example 1 using the carbon particles subjected to the above oxidation treatment and silane coupling treatment. Using this composite plating solution, electroplating is performed at a liquid temperature of 25 ° C. and a current density of 1.5 A / dm 2 , and a composite of silver and carbon particles having a film thickness of 15 μm is formed on a copper plate having a thickness of 0.3 mm as a material. A composite plating material on which a plating film was formed was produced.
得られた複合めっき材について、実施例１と同様の方法により、めっき皮膜中の炭素の含有量を算出し、摩擦係数を測定し、耐摩耗性の評価を行った。その結果、めっき皮膜中の炭素の含有量は０．３質量％であり、摩擦係数は、摺動初期で０．４０〜０．５０、摺動が進むと０．４５〜０．７０になった。また、６千回の往復摺動動作後に素材が露出した。 About the obtained composite plating material, the carbon content in the plating film was calculated by the same method as in Example 1, the friction coefficient was measured, and the wear resistance was evaluated. As a result, the carbon content in the plating film is 0.3% by mass, and the coefficient of friction is 0.40 to 0.50 at the beginning of sliding, and 0.45 to 0.70 as sliding proceeds. It was. The material was exposed after 6,000 reciprocating sliding operations.
［比較例３］
実施例１と同様の炭素粒子についてＢｒｏｄｉｅ法による酸化処理を行った。すなわち、実施例１と同様の炭素粒子１２質量％を塩素酸ナトリウムに添加した後、塩素酸ナトリウムに対して１００質量％の硝酸を添加し、この混合溶液を６０℃に加熱して１時間攪拌した。この反応液に蒸留水を加えた後、水酸化ナトリウムを添加した。その後、炭素粒子をろ別した後、７０℃で２４時間乾燥させた。この酸化処理後の炭素粒子の表面電位について実施例１と同様の方法により測定したところ、等電点はｐＨ２以下であった。
[Comparative Example 3]
The same carbon particles as in Example 1 were subjected to an oxidation treatment by the Brodie method. That is, after adding 12% by mass of carbon particles similar to Example 1 to sodium chlorate, 100% by mass of nitric acid was added to sodium chlorate, and this mixed solution was heated to 60 ° C. and stirred for 1 hour. did. Distilled water was added to the reaction solution, and then sodium hydroxide was added. Thereafter, the carbon particles were filtered off and dried at 70 ° C. for 24 hours. When the surface potential of the carbon particles after the oxidation treatment was measured by the same method as in Example 1, the isoelectric point was pH 2 or less.
次に、上記の湿式酸化処理を行った炭素粒子１０質量％をエタノール中に分散させて懸濁させ、この炭素粒子の懸濁液を６０℃に加熱して攪拌しながら、シランカップリング剤として３−アミノプロピルトリメトキシシラン（エタノールの５体積％）を添加した後、２４時間攪拌してシランカップリング処理を行った。その後、炭素粒子をトルエンで洗浄し、７０℃で４８時間乾燥させた。このように酸化処理およびシランカップリング処理を施した炭素粒子の表面電位について実施例１と同様の方法により測定したところ、等電点はｐＨ８になった。 Next, 10% by mass of the carbon particles subjected to the above wet oxidation treatment are dispersed and suspended in ethanol, and the suspension of the carbon particles is heated to 60 ° C. while stirring and used as a silane coupling agent. After adding 3-aminopropyltrimethoxysilane (5% by volume of ethanol), the mixture was stirred for 24 hours for silane coupling treatment. Thereafter, the carbon particles were washed with toluene and dried at 70 ° C. for 48 hours. The surface potential of the carbon particles subjected to oxidation treatment and silane coupling treatment as described above was measured by the same method as in Example 1. As a result, the isoelectric point was pH 8.
次に、上記の酸化処理およびシランカップリング処理を施した炭素粒子を使用して、実施例１と同様の方法により複合めっき液を作製した。この複合めっき液を使用して、液温２５℃、電流密度１．５Ａ／ｄｍ２で電気めっきを行い、素材としての厚さ０．３ｍｍの銅板上に膜厚１５μｍの銀と炭素粒子の複合めっき皮膜が形成された複合めっき材を作製した。 Next, a composite plating solution was produced by the same method as in Example 1 using the carbon particles subjected to the above oxidation treatment and silane coupling treatment. Using this composite plating solution, electroplating is performed at a liquid temperature of 25 ° C. and a current density of 1.5 A / dm 2 , and a composite of silver and carbon particles having a film thickness of 15 μm is formed on a copper plate having a thickness of 0.3 mm as a material. A composite plating material on which a plating film was formed was produced.
得られた複合めっき材について、実施例１と同様の方法により、めっき皮膜中の炭素の含有量を算出し、摩擦係数を測定し、耐摩耗性の評価を行った。その結果、めっき皮膜中の炭素の含有量は０．３質量％であり、摩擦係数は、摺動初期で０．６０〜０．７０、摺動が進むと０．７０〜０．９０になった。また、４千回の往復摺動動作後に素材が露出した。 About the obtained composite plating material, the carbon content in the plating film was calculated by the same method as in Example 1, the friction coefficient was measured, and the wear resistance was evaluated. As a result, the carbon content in the plating film is 0.3% by mass, and the coefficient of friction is 0.60 to 0.70 at the beginning of sliding, and 0.70 to 0.90 when sliding proceeds. It was. The material was exposed after 4,000 reciprocating sliding operations.
Claims (8)
A composite plating solution, wherein carbon particles subjected to an oxidation treatment and a silane coupling treatment are added to a silver plating solution for silver-plating a material.
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